CN104350179A - 用于制备含氧化铟的层的方法 - Google Patents
用于制备含氧化铟的层的方法 Download PDFInfo
- Publication number
- CN104350179A CN104350179A CN201380030864.1A CN201380030864A CN104350179A CN 104350179 A CN104350179 A CN 104350179A CN 201380030864 A CN201380030864 A CN 201380030864A CN 104350179 A CN104350179 A CN 104350179A
- Authority
- CN
- China
- Prior art keywords
- alkoxide
- indium
- layer
- oxo bridge
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910003437 indium oxide Inorganic materials 0.000 title abstract description 13
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 67
- 229910052738 indium Inorganic materials 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 6
- 239000008199 coating composition Substances 0.000 claims abstract description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 48
- 238000002360 preparation method Methods 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012702 metal oxide precursor Substances 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 8
- 238000004528 spin coating Methods 0.000 claims description 8
- 125000000962 organic group Chemical group 0.000 claims description 7
- 238000007669 thermal treatment Methods 0.000 claims description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 5
- 238000007639 printing Methods 0.000 claims description 5
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000010 aprotic solvent Substances 0.000 claims description 3
- 230000005499 meniscus Effects 0.000 claims description 3
- 125000004171 alkoxy aryl group Chemical group 0.000 claims description 2
- 125000005055 alkyl alkoxy group Chemical group 0.000 claims description 2
- 125000005248 alkyl aryloxy group Chemical group 0.000 claims description 2
- 238000007766 curtain coating Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 abstract description 3
- 229910016287 MxOy Inorganic materials 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- -1 indium alkoxide Chemical class 0.000 description 27
- 239000002184 metal Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000002585 base Substances 0.000 description 13
- 239000002243 precursor Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- CHLICZRVGGXEOD-UHFFFAOYSA-N 1-Methoxy-4-methylbenzene Chemical compound COC1=CC=C(C)C=C1 CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000005670 electromagnetic radiation Effects 0.000 description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical class [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- OSIGJGFTADMDOB-UHFFFAOYSA-N 1-Methoxy-3-methylbenzene Chemical compound COC1=CC=CC(C)=C1 OSIGJGFTADMDOB-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 229940077398 4-methyl anisole Drugs 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 229910021617 Indium monochloride Inorganic materials 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 229910001449 indium ion Inorganic materials 0.000 description 2
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229940095102 methyl benzoate Drugs 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- YNOGYQAEJGADFJ-UHFFFAOYSA-N oxolan-2-ylmethanamine Chemical compound NCC1CCCO1 YNOGYQAEJGADFJ-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 238000001429 visible spectrum Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- HZTAHAGYTNKCHH-WAYWQWQTSA-N C/N=C1\[O]=CCC1 Chemical compound C/N=C1\[O]=CCC1 HZTAHAGYTNKCHH-WAYWQWQTSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 244000287680 Garcinia dulcis Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 108700031620 S-acetylthiorphan Proteins 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002471 indium Chemical class 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000013532 laser treatment Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004831 organic oxygen compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
-
- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及一种制备含氧化铟的层的液相法,其中将组合物施加于基材上,任选地干燥和转化成含氧化铟的层,所述组合物包含至少一种通式MxOy(OR)z[O(R’O)eH]aXbYc[R’’OH]d的铟氧桥醇盐和至少一种溶剂,其中x=3-25,y=1-10,z=3-50,a=0-25,b=0-20,c=1-20,d=0-25,e=0、1,M=In,R、R’、R’’=有机基团,X=F、Cl、Br、I,且Y=-NO3、-NO2,其中b+c=1–20,涉及所述通式的铟氧桥醇盐,涉及包含它们的涂料组合物,涉及通过根据本发明的方法可制备的层,并涉及它们的用途。
Description
本发明涉及用于制备含氧化铟的层的方法,涉及可用在所述方法中的前体和涂料组合物,涉及可用所述方法生产的层,和涉及它们的用途。
由于在3.6和3.75eV之间的大的带隙(对蒸镀层所测量的)[H.S. Kim, P.D. Byrne, A. Facchetti, T.J. Marks; J. Am. Chem. Soc.2008, 130, 12580-12581],氧化铟(氧化铟(III),In2O3)是一种大有前途的半导体。此外,几百纳米厚度的薄膜能够在可见光谱范围内在550nm处具有大于90%的高透明度。在极端高度有序的氧化铟单晶中,另外还可测量最高160cm2/Vs的载流子迁移速率。
氧化铟常常特别是与氧化锡(IV)(SnO2)一起作为半导电的混合氧化物ITO使用。此外,由于ITO层相对高的导电性同时在可见光谱范围内具有透明度,它们尤其在液晶显示器(LCD)领域使用,特别是作为“透明电极”。这些大都被掺杂的金属氧化物层在工业上特别是在高真空下通过昂贵的蒸镀法制备。
因此,含氧化铟的层及其制备,尤其是ITO层和纯的氧化铟层及其制备对于半导体-和显示器工业来说是十分重要的。
作为用于合成含氧化铟的层的可能的反应物或前体已经讨论了多个化合物种类。例如包括铟盐。例如,Marks等人描述了用包括溶解在甲氧基乙醇中的InCl3和碱单乙醇胺(MEA)的前体溶液制备的组件。在溶液旋涂之后,通过在400℃下热处理得到相应的氧化铟层[H.S. Kim, P.D. Byrne, A. Facchetti, T.J. Marks; J. Am. Chem. Soc.2008, 130, 12580-12581和补充信息]。
在另一处,讨论了铟醇盐作为用于氧化铟合成的可能的反应物或前体。铟醇盐意指由如下组成的化合物:至少一个铟原子、至少一个式-OR (R =有机基团)的醇盐基团和任选地一个或多个有机基团-R、一个或多个卤素基团和/或一个或多个-OH或-OROH基团。
独立于用于氧化铟形成的可能用途,现有技术中描述了各种铟醇盐和铟氧桥醇盐。与已经提到的铟醇盐相比,铟氧桥醇盐还具有至少一个直接结合到铟原子上或桥接至少两个铟原子的另外的氧基团(桥氧基)。
Mehrotra等人描述了用Na-OR由氯化铟(III)(InCl3)制备铟三醇盐In(OR)3,其中R是甲基、乙基、异丙基、正-、仲-、叔-丁基和戊基。[S. Chatterjee, S. R. Bindal, R.C. Mehrotra; J. Indian Chem. Soc. 1976, 53, 867]。
Carmalt等人的综述文章(Coordination Chemistry Reviews 250 (2006), 682-709)描述了各种镓(III)-和铟(III)醇盐和-芳基氧化物,其部分也可通过烷氧基团桥接存在。另外介绍了式In5( μ-O)(OiPr)13的氧中心簇群,更具体来说是[In5( μ5-O)( μ3-OiPr)4( μ2-OiPr)4(OiPr)5],其为一种氧桥醇盐且不能由[In(OiPr)3]制备。
N.Turova等人的综述文章,Russian Chemical Reviews 73 (11), 1041-1064 (2004)总结了金属氧桥醇盐的合成、性能和结构,其中认为这些是通过溶胶-凝胶技术制备氧化物材料的前体。除了多种其它化合物之外,还描述了[Sn3O(OiBu)10(iBuOH)2]、已经提及的化合物[In5O(OiPr)13]和[Sn6O4(OR)4](R=Me,Pri)的合成和结构。
N. Turova等人的文章Journal of Sol-Gel Science and Technology, 2, 17-23 (1994)展示了对醇盐的研究结果,其中认为这些是开发醇盐和醇盐基粉末的溶胶-凝胶法的科学基础。在该文章上下文中,还特别讨论了所认为的"异丙醇铟”,已证实其是式M5( μ-O)(OiPr)13的带有中心氧原子和五个环绕的金属原子的氧桥醇盐,这在Carmalt等人的文章中也进行了描述。
此化合物的合成及其晶体结构被Bradley等人在J. Chem. Soc., Chem. Commun., 1988, 1258-1259中进行了描述。作者的进一步研究得到的结果显示此化合物的形成不能认为是中间形成的In(OiPr)3的水解造成的(Bradley等人,Polyhedron第9卷,No. 5,第719-726页,1990)。Suh等人在J. Am. Chem. Soc. 2000, 122, 9396-9404中另外还发现此化合物也不能通过热途径由In(OiPr)3制备。另外,Bradley (Bradley等人,Polyhedron第9卷,No. 5,第719-726页,1990)发现此化合物不能升华。
金属氧化物层原则上可通过各种方法制备。
制备金属氧化物层的一种可能性基于溅射技术。然而,这些技术具有的缺点在于它们必须在高真空下进行。另外的缺点在于由其制备的膜具有许多氧缺陷,这使其不可能建立该层的受控和可重现的化学计量并因此导致制得的层性能较差。
用于制备金属氧化物层的另外的原则上的可能性是基于化学气相沉积。因此例如,可通过气相沉积由氧化铟前体如铟醇盐或铟氧桥醇盐制备含氧化铟的层。例如US 6,958,300 B2教导在通过气相沉积(例如CVD或ALD)进行半导体或金属氧化物层的制备中使用通式M1 q(O)x(OR1)y (q=1-2;x=0-4,y=1-8,M1=金属;例如Ga、In或Zn,R1=有机基团;当x=0时为醇盐,当≥1时为氧桥醇盐)的至少一种金属有机氧化物前体(醇盐或氧桥醇盐)。然而,所有的气相沉积方法都具有如下缺点:它们i)在热反应机制的情况下,需要使用非常高的温度,或ii)在以电磁辐射形式引入用于前体分解需要的能量的情况下,需要高的能量密度。在两种情况下,只有通过非常高的设备投入才能以受控和同一的方式引入分解前体需要的能量。
因此有利地通过液相法制备金属氧化物层,即通过在转化成金属氧化物之前包括至少一个将要涂覆的基材用至少一种金属氧化物前体的液体溶液进行涂覆的工艺步骤的方法,任选地随后将其干燥和转化。金属氧化物前体在此理解为是可热分解或可用电磁辐射分解的化合物,用该化合物可以在存在或不存在氧或其它氧化物质的条件下形成含金属氧化物的层。金属氧化物前体的突出的例子是例如金属醇盐和金属氧桥醇盐。原则上,所述层在此可以i)通过溶胶-凝胶法制备,其中所使用的金属醇盐在水存在下通过水解和随后缩合首先转化成凝胶,然后转化成金属氧化物,或ii)经由转化从非水溶液制备。
由液相从铟醇盐制备含氧化铟的层也属于现有技术。
在大量水存在下通过溶胶-凝胶法由铟醇盐制备含氧化铟的层属于现有技术。WO 2008/083310 A1描述了在基材上制备无机层或有机/无机混杂层的方法,其中将金属醇盐(例如通式R1M-(OR2)y-x之一)或其预聚物施加到基材上,然后所产生的金属醇盐层在水存在下并与水反应固化。可用的金属醇盐尤其可以是铟、镓、锡或锌的那些醇盐。然而,可根据该方法生产的含氧化铟的层是非常不均匀的,不具有令人满意的电性能,另外,在大气影响和电应力方面不足够稳定。
JP 2007-042689 A描述了可含有铟醇盐的金属醇盐溶液,以及制备使用这些金属醇盐溶液的半导体组件的方法。热处理该金属醇盐膜并转化成氧化物层;然而,这些系统也未提供具有足够好的电性能和在大气影响和电应力方面具有足够稳定性的足够均匀的膜。另外,纯的氧化铟层不能通过其中描述的方法制备。
WO 2010/094581 A1描述了使用铟醇盐用于由无水溶液制备含氧化铟的层。尽管所得的层比通过溶胶-凝胶法制备的层更均匀,但是在无水体系中使用铟醇盐仍然还具有如下缺点:含铟醇盐的制剂转化成含氧化铟的层未赋予所产生的层足够好的电性能和在大气影响和电应力方面足够的稳定性。
WO 2011/072887 A1公开了一种用于制备通式InX(OR)2的铟卤素二醇盐的方法,并且WO 2011/073005 A2公开了使用包含至少一种这样的铟卤素二醇盐InX(OR)2的组合物制备含氧化铟的层的液相法。然而,所产生的含铟醇盐的层(尽管电性能相对于到目前为止引用的现有技术已经改进)仍然不具有足够好的电性能或在大气影响和电应力方面足够的稳定性。这可能可以归因于,添入了氯化物基团,导致所得金属氧化物半导体中的氧的化合价饱和,并因此导致电子迁移率下降(Jeong等人, J. Phys. Chem. C 2011, 115, 11773-11780)。
根据WO 2010/122274 A1,尽管通过添加碱金属或碱土金属提高了金属氧化物半导体的稳定性,但是所得层不具有良好的半导电性能。
最后,WO 2011/020781 A1描述了使用包含通式MxOy(OR)z[O(R’O)cH]aXb[R’’OH]d的铟氧桥醇盐的组合物制备含氧化铟的层的液相法,该方法产生具有受控的、一致的和可再现的化学计量、高均匀性和更好的电性能的氧化铟层。然而缺点是,这些含氧化铟的层也尚未产生足够好的电性能,尤其是在大气影响(尤其是对含于大气中的氧和/或水)和电应力(尤其是在负偏置应力下仍然稳定性不足)方面尚未产生足够的稳定性。
因此,本发明的目的是,提供避免了现有技术的缺点的用于制备含氧化铟的层的方法。更具体地,在此将提供产生具有受控的、一致的和可再现的化学计量、高均匀性、好的电性能和在大气影响和电应力方面好的稳定性的氧化铟层的方法。
所述目的通过用于制备含氧化铟的层的液相法实现,在所述液相法中,将组合物施加于基材上,任选地干燥并转化成含氧化铟的层,所述组合物包含i)至少一种通式MxOy(OR)z[O(R’O)eH]aXbYc[R’’OH]d的铟氧桥醇盐,其中M = In,x = 3 - 25,y = 1 - 10,z = 3 - 50,a = 0 - 25,b = 0 - 20,c = 1 - 20,d = 0 - 25,e = 0、1,R、R’、R’’=有机基团,X = F、Cl、Br、I,且Y = -NO3、-NO2,条件是,b + c = 1 - 20,和ii)至少一种溶剂。优选的基团R、R’和R’’是C1-C15-烷基、-烷氧基烷基、-芳基或-氧基芳基烷基(其中前缀C1-C15分别代表具有1-15个碳原子的基团),且特别优选的基团R、R’和R’’是-CH3、-CH2CH3、-CH2CH2OCH3、-CH(CH3)2、-CH(CH3)CH2OCH3、-C(CH3)3和
。
根据本发明的由溶液制备含氧化铟的层的液相法是包括至少一个这样的工艺步骤的方法:在所述工艺步骤中,用含有至少一种金属氧化物前体的液体溶液涂覆要涂覆的基材,然后任选地干燥。更具体地,这不是溅射-或CVD方法。根据本发明的液相法可以用非水性组合物施行,或者作为溶胶-凝胶法用水性组合物施行。根据本发明的方法优选地是无水方法。金属氧化物前体被理解为是指可热分解或可用电磁辐射分解的化合物,可以在存在或不存在氧或其它氧化物质的条件下用该化合物形成含金属氧化物的层。液体组合物在本发明的上下文中应理解为是指这样的组合物:其在SATP条件(“标准环境温度和压力”;T = 25℃和p = 1013 hPa)下和在施用到要涂覆的基材上时是液体。非水性溶液或无水组合物在这里和在下文中被理解为是指具有不超过200 ppm的H2O的溶液或制剂。相应地,水性组合物具有高于此的含水量。
根据本发明方法的方法产物,即含氧化铟的层,应理解为是具有主要以氧化物形式存在的铟原子或铟离子的含金属或含半金属的层。任选地,所述含氧化铟的层也还可以具有来自未完全转化或未完全除去所产生的副产物的碳烯-、卤素-或醇盐成分。该含氧化铟的层可以是纯的氧化铟层,即:在不考虑可能的碳烯-、醇盐-或卤素成分的情况下,主要由氧化物形式的铟原子或铟离子组成,或成比例地还具有可以本身以单质形式或氧化物形式存在的其它金属。为了产生纯的氧化铟层,在根据本发明的方法中应当仅使用含铟的前体,优选地仅使用铟氧桥醇盐化合物和任选地使用铟醇盐。相反,为了产生除了含铟前体之外还含有其它金属的层,也可使用氧化态为0的金属的前体(以制备含有其它中性形式的金属的层)或金属氧化物-前体(例如其它金属醇盐或-氧桥醇盐)。
可以如下制备迄今为止在文献中尚未描述过的本发明的通式MxOy(OR)z[O(R’O)eH]aXbYc[R’’OH]d的前体:例如,通过AgNO3或具有在反应介质中其阳离子形成微溶氯化物的趋势的离子化合物与在现有技术中已知的化合物MxOy(OR)z[O(R’O)cH]aXb[R’’OH]d反应,其中x = 3 - 25,y = 1 - 10,z = 3 - 50,a = 0 - 25,b = 0 - 20,c = 0、1,d = 0 - 25,M = In,R、R’、R’’=有机基团,且X = F、Cl、Br、I。也合适的是,In6O2X6(OR)6(R’CH(O)COOR’’)2(HOR)x(HNR’’’2)y (参见WO 2012/010427 A1)或In7O2(OH)(OR)12X4(ROH)x (参见WO 2012/010464 A1)与相同试剂的反应。也合适的是,由可根据WO 2011/072887 A1制备的通式InX(OR)2的含卤素的铟卤素二醇盐合成。
特别稳定的层可以用基本上不再具有任何卤素基团的铟氧桥醇盐实现,即用通式MxOy(OR)z[O(R’O)eH]aXbYc[R’’OH]d(其中b = 0)的那些化合物实现。
优选地,所述铟氧桥醇盐是通式MxOy(OR)zYc的一种,其中x = 3 - 20,y = 1 - 8,z = 3 - 25,c = 1 - 20,OR = C1-C15-烷氧基、-氧基烷基烷氧基、-芳基氧基或-氧基芳基烷氧基,Y = -NO3,和特别优选是通式MxOy(OR)zYc的一种,其中x = 3 - 15,y = 1 - 5,z = 10 - 20,c = 4 - 10,R = = -CH3、-CH2CH3、-CH2CH2OCH3、-CH(CH3)2、-CH(CH3)CH2OCH3、-C(CH3)3和/或
且Y = -NO3。这些具有以下优点:适合用于制备在大气影响和电应力方面具有特别好稳定性的层。
非常特别优选的是这样的方法,其中所使用的铟氧桥醇盐可从通式In(OCH3)2Cl的反应物制备。
当使用铟氧桥醇盐作为唯一的金属氧化物前体时,根据本发明的方法特别好地适合用于制备氧化铟层。当所述唯一的金属氧化物前体具有通式In6O(OCH2CH2OCH3)10(NO3)6时,产生非常特别好的层。
所述至少一种铟氧桥醇盐优选以基于所述组合物的总质量计0.1-15重量%、特别优选1-10重量%、非常特别优选2-5重量%的比例存在。
所述组合物进一步含有至少一种溶剂,即所述组合物可含有一种溶剂或不同溶剂的混合物。优选可用于根据本发明方法的制剂中的是非质子溶剂和弱质子溶剂,即:选自非质子非极性溶剂的那些,即:烷烃、取代的烷烃、烯烃、炔烃、没有或带有脂肪族或芳族取代基的芳烃、卤代烃、四甲基硅烷;选自非质子极性溶剂的那些,即:醚、芳族醚、取代的醚、酯或酸酐、酮、叔胺、硝基甲烷、DMF(二甲基甲酰胺)、DMSO(二甲基亚砜)或异丙二醇碳酸酯;和弱质子溶剂,即:醇、伯胺和仲胺以及甲酰胺。特别优选可用的溶剂是醇以及甲苯、二甲苯、茴香醚、均三甲苯、正己烷、正庚烷、三-(3,6-二氧杂庚基)胺(TDA)、2-氨基甲基四氢呋喃、苯乙醚、4-甲基茴香醚、3-甲基茴香醚、苯甲酸甲酯、N-甲基-2-吡咯烷酮(NMP)、四氢化萘、苯甲酸乙酯和乙醚。非常特别优选的溶剂是甲醇、乙醇、异丙醇、四氢糠醇、1-甲氧基-2-丙醇、叔丁醇和甲苯以及它们的混合物。
为了实现特别好的可印刷性或可涂覆性,根据本发明的方法中使用的组合物优选具有1mPa.s至10Pa.s、尤其是1mPa.s至100mPa.s的粘度,根据DIN 53019第1至2部分测定和在20℃下测量。相应的粘度可通过加入聚合物、纤维素衍生物或例如可以以Aerosil的商品名得到的SiO2,和尤其是通过PMMA、聚乙烯醇、氨基甲酸酯增稠剂或聚丙烯酸酯增稠剂来调节。
在根据本发明的方法中使用的基材优选是由玻璃、硅、二氧化硅、金属氧化物或过渡金属氧化物、金属或聚合物材料,尤其是PI或PET构成的基材。
根据本发明的方法特别有利地是选自下述方法的涂覆方法:印刷方法(尤其是柔版印刷/凹版印刷、喷墨印刷、胶版印刷、数字胶版印刷和丝网印刷)、喷雾法、旋转涂覆法(“旋涂”)、浸渍法(“浸涂”)和选自弯月面(Meniscus)涂覆、狭缝涂覆、槽模(Slot-Die)涂覆和幕涂的方法。根据本发明的涂覆方法最优选印刷方法。
在涂覆后和转化前,可另外将经涂覆的基材干燥。用于此目的的相应的措施和条件是本领域技术人员已知的。
可以以热途径和/或通过用电磁辐射尤其是光化辐射的照射进行向含氧化铟的层的转化。优选通过大于150℃的温度以热途径进行转化。然而,当使用250℃至360℃的温度进行转化时,可以实现特别好的结果。
在此,通常使用几秒到几小时的转化时间。
此外,可以通过在热处理之前、过程中或之后辐照UV-、IR-或VIS-辐射或用空气或氧处理涂覆过的基材促进热转化。
此外,可通过在转化步骤之后进行的组合的温度处理和气体处理(用H2或O2)、等离子体处理(Ar-、N2、O2或H2-等离子体)、激光处理(用在UV、VIS或IR范围的波长)或臭氧处理,进一步改善根据本发明的方法制得的层的品质。
本发明的主题还是迄今为止在文献中尚未描述的通式MxOy(OR)z[O(R’O)eH]aXbYc[R’’OH]d的铟氧桥醇盐,其中M = In,x = 3 - 25,y = 1 - 10,z = 3 - 50,a = 0 - 25,b = 0 - 20,c = 1 - 20,d = 0 - 25,e = 0、1,R、R’、R’’=有机基团,X = F、Cl、Br、I,且Y = -NO3、-NO2,其中b + c = 1–20,和在上面已经描述过的从文献同样未知的其优选形式,以及具有至少一种本发明的铟氧桥醇盐和至少一种溶剂的涂料组合物。
所述组合物在此可以包含一种溶剂或不同溶剂的混合物。优选可用于根据本发明方法的制剂中的是非质子溶剂和弱质子溶剂,即:选自非质子非极性溶剂的那些,即:烷烃、取代的烷烃、烯烃、炔烃、没有或带有脂肪族或芳族取代基的芳烃、卤代烃、四甲基硅烷;选自非质子极性溶剂的那些,即:醚、芳族醚、取代的醚、酯或酸酐、酮、叔胺、硝基甲烷、DMF(二甲基甲酰胺)、DMSO(二甲基亚砜)或异丙二醇碳酸酯;和弱质子溶剂,即:醇、伯胺和仲胺以及甲酰胺。特别优选可用的溶剂是醇以及甲苯、二甲苯、茴香醚、均三甲苯、正己烷、正庚烷、三-(3,6-二氧杂庚基)胺(TDA)、2-氨基甲基四氢呋喃、苯乙醚、4-甲基茴香醚、3-甲基茴香醚、苯甲酸甲酯、N-甲基-2-吡咯烷酮(NMP)、四氢化萘、苯甲酸乙酯和乙醚。非常特别优选的溶剂是甲醇、乙醇、异丙醇、四氢糠醇、1-甲氧基-2-丙醇、叔丁醇和甲苯以及它们的混合物。
本发明的主题还是可通过根据本发明的方法制备的含氧化铟的层。通过根据本发明的方法可制备的含氧化铟的层具有特别好的性能,并且是纯的氧化铟层。
通过根据本发明的方法可制备的含氧化铟的层有利地适合用于制备电子部件,特别是制备晶体管(特别是薄膜晶体管)、二极管、传感器或太阳能电池。
下面的实施例意在详细地解释本发明的主题。
实施例:
实施例1
合成
a) 在甲醇中合成本发明的物质
在排除空气氧的情况下进行合成。
将25 g (1.0重量%)的铟氯二甲醇盐溶解在3 L无水甲醇中。随后,加入17.62 g硝酸银,并将混合物在避光下搅拌12 h。将形成的固体(副产物)滤出,并将澄清溶液在真空下在40℃蒸发浓缩。将剩余的固体(产物)在1毫巴下干燥12 h并装入容器中。
b)在2-甲氧基乙醇中合成本发明的物质
在排除空气氧的情况下进行合成。
将2.5 g (4.9重量%)的铟氯二甲醇盐溶解在50 ml无水2-甲氧基乙醇中。随后,加入1.76 g硝酸银,并在避光下搅拌12 h。将形成的固体(副产物)滤出,并将澄清溶液在真空下在40℃蒸发浓缩。将剩余的固体(产物)在1毫巴下干燥12 h并装入容器中。
c)在四氢糠醇中合成本发明的物质
在排除空气氧的情况下进行合成。
将2.5 g (4.5重量%)的铟氯二甲醇盐溶解在50 ml无水四氢糠醇中。随后,加入1.76 g硝酸银,并在避光下搅拌>12 h。将形成的固体(副产物)滤出,并将澄清溶液在真空下在40℃蒸发浓缩。将剩余的固体(产物)在1毫巴下干燥12 h并装入容器中。
实施例2
TFT的加工和应力试验
a)本发明的实施例
通过旋涂(2000 rpm,30s),用100μl 5重量%溶液(其含有根据实施例1b)形成的在2-甲氧基乙醇中的产品)涂覆经掺杂的硅基材,所述硅基材具有约15 mm的边长且具有约200 nm厚的氧化硅涂层和ITO/金的指结构。涂覆过程之后,将该涂覆过的基材在空气下在350℃的温度下热处理1 h。
用聚二甲基硅氧烷(PDMSi)层钝化该半导体层。借助旋涂来施加BuOH的PDMSi的溶液,然后将样品在350℃热处理1 h。
a)对比实施例
通过旋涂(2000 rpm,30s),用100μl 5重量%溶液(其含有在2-甲氧基乙醇中的铟氯二甲醇盐)涂覆经掺杂的硅基材,所述硅基材具有约15 mm的边长且具有约200 nm厚度的氧化硅涂层和ITO/金的指结构。涂覆操作以后,将该涂覆过的基材在空气下在350℃的温度下热处理1 h。用聚二甲基硅氧烷(PDMSi)层钝化该半导体层。借助旋涂来施加BuOH的PDMSi的溶液,然后将样品在350℃热处理1 h。
在负偏置应力(Vgs = -20V,Vds = 5V,t = 4000s)下,本发明的涂层(参见图1)显示比对比层(图2)更好的电稳定性。起始电压的移动是-3.5V和-7.5V。另外,本发明的涂层尤其对大气影响具有更好的稳定性。
这2幅图显示了在Vds = 10V时各自的传输特征线;TFT (2000μm通道宽度和20μm通道长度)。
Claims (15)
1.用于制备含氧化铟的层的液相法,
其特征在于,
将包含以下物质的组合物施加于基材上,任选地干燥并转化成含氧化铟的层:
i) 至少一种通式MxOy(OR)z[O(R’O)eH]aXbYc[R’’OH]d的铟氧桥醇盐
其中 x = 3 - 25,
y = 1 - 10,
z = 3 - 50,
a = 0 - 25,
b = 0 - 20,
c = 1 - 20,
d = 0 - 25,
e = 0、1,
M = In,
R、R’、R’’=有机基团,
X = F、Cl、Br、I,
Y = -NO3、-NO2、
条件是,b + c = 1–20,和
ii) 至少一种溶剂。
2.根据权利要求1所述的方法,
其特征在于,
作为至少一种铟氧桥醇盐使用式MxOy(OR)zYc的氧桥醇盐,其中x = 3 - 20,y = 1 - 8,z = 3 - 25,c = 1 - 20,OR = C1-C15-烷氧基、-氧基烷基烷氧基、-芳基氧基或-氧基芳基烷氧基,且Y = -NO3;
特别优选通式MxOy(OR)zYc的这样的氧桥醇盐之一,其中x = 3 - 15,y = 1 - 5,z = 10 - 20,c = 4 - 10,
R = -CH3、-CH2CH3、-CH2CH2OCH3、-CH(CH3)2、-CH(CH3)CH2OCH3、-C(CH3)3和/或
,
且Y = NO3。
3.根据前述权利要求中的任一项所述的方法,
其特征在于,
所述至少一种铟氧桥醇盐是在所述方法中使用的唯一金属氧化物前体。
4.根据前述权利要求中的任一项所述的方法,
其特征在于,
所述至少一种铟氧桥醇盐以基于所述组合物的总质量计0.1-15重量%的比例存在。
5.根据前述权利要求中的任一项所述的方法,
其特征在于,
所述至少一种溶剂是非质子溶剂或弱质子溶剂。
6.根据权利要求5所述的方法,
其特征在于,
所述至少一种溶剂选自甲醇、乙醇、异丙醇、四氢糠醇、1-甲氧基-2-丙醇、叔丁醇和甲苯。
7.根据前述权利要求中的任一项所述的方法,
其特征在于,
所述组合物具有1 mPa·s至10 Pa·s的粘度。
8.根据前述权利要求中的任一项所述的方法,
其特征在于,
所述基材由玻璃、硅、二氧化硅、金属氧化物或过渡金属氧化物、金属或聚合物材料组成。
9.根据前述权利要求中的任一项所述的方法,
其特征在于,
通过涂覆方法、印刷方法、喷涂方法、旋转涂覆方法、浸渍方法或选自弯月面涂覆、狭缝涂覆、槽模涂覆和幕涂的方法,将所述无水组合物施加于所述基材上。
10.根据前述权利要求中的任一项所述的方法,
其特征在于,
所述转化通过高于150℃的温度加热进行。
11.根据权利要求10所述的方法,
其特征在于,
在所述热处理之前、过程中或之后照射UV-、IR-或VIS-辐射。
12.通式MxOy(OR)z[O(R’O)eH]aXbYc[R’’OH]d的铟氧桥醇盐
其中 x = 3 - 25,
y = 1 - 10,
z = 3 - 50,
a = 0 - 25,
b = 0 - 20,
c = 1 - 20,
d = 0 - 25,
e = 0、1,
M = In,
R、R’、R’’=有机基团,
X = F、Cl、Br、I,
Y = -NO3、-NO2,
条件是,b + c = 1 - 20。
13.涂料组合物,其包含至少一种根据权利要求12所述的铟氧桥醇盐和至少一种溶剂。
14.含氧化铟的层,其可通过根据权利要求1-11所述的方法制备。
15.至少一种根据权利要求14所述的含氧化铟的层用于制备电子部件,特别是用于制备晶体管、二极管、传感器或太阳能电池的用途。
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DE102013212017A1 (de) | 2013-06-25 | 2015-01-08 | Evonik Industries Ag | Verfahren zur Herstellung von Indiumalkoxid-Verbindungen, die nach dem Verfahren herstellbaren Indiumalkoxid-Verbindungen und ihre Verwendung |
DE102013212019A1 (de) | 2013-06-25 | 2015-01-08 | Evonik Industries Ag | Formulierungen zur Herstellung Indiumoxid-haltiger Schichten, Verfahren zu ihrer Herstellung und ihre Verwendung |
WO2015019771A1 (ja) | 2013-08-09 | 2015-02-12 | 国立大学法人北陸先端科学技術大学院大学 | 酸化物半導体層及びその製造方法、並びに酸化物半導体の前駆体、酸化物半導体層、半導体素子、及び電子デバイス |
DE102014202718A1 (de) | 2014-02-14 | 2015-08-20 | Evonik Degussa Gmbh | Beschichtungszusammensetzung, Verfahren zu ihrer Herstellung und ihre Verwendung |
EP3342900A1 (de) * | 2016-12-27 | 2018-07-04 | Evonik Degussa GmbH | Zusammensetzung zur reinigung sowie verhinderung von ablagerungen in beschichtungsdüsen für lösungsprozessierbare metalloxid-präkursoren |
JP6795543B2 (ja) * | 2018-04-27 | 2020-12-02 | 株式会社Joled | 半導体装置の製造方法 |
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- 2013-06-04 EP EP13726540.1A patent/EP2861782B1/de not_active Not-in-force
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Also Published As
Publication number | Publication date |
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EP2861782B1 (de) | 2016-03-09 |
TWI600726B (zh) | 2017-10-01 |
RU2639169C2 (ru) | 2017-12-20 |
WO2013186082A3 (de) | 2014-08-07 |
JP2015522509A (ja) | 2015-08-06 |
KR20150024331A (ko) | 2015-03-06 |
CN104350179B (zh) | 2016-12-07 |
DE102012209918A1 (de) | 2013-12-19 |
KR102032168B1 (ko) | 2019-10-15 |
WO2013186082A9 (de) | 2014-02-13 |
US9293326B2 (en) | 2016-03-22 |
JP6195916B2 (ja) | 2017-09-13 |
EP2861782A2 (de) | 2015-04-22 |
WO2013186082A2 (de) | 2013-12-19 |
RU2015100052A (ru) | 2016-08-10 |
US20150170913A1 (en) | 2015-06-18 |
TW201420697A (zh) | 2014-06-01 |
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